Mechanochemical Based Synthesis of Perfluoropyridine Monomers for Polymerization

ABSTRACT

The present invention relates to a mechanochemical based synthesis of perfluoropyridine monomers, polymers made using such monomers and methods of making and using articles comprising such polymers. Such perfluoropyridine monomers are easily chemically tuned have the strength needed for high temperature applications and the flexibility needed for low temperature applications. In addition, to the aforementioned monomers, a mechanochemical based synthesis for such perfluoropyridine monomers is provided. All of the aforementioned performance application advantages are also found in polymers comprising Applicants&#39; perfluoropyridine monomers.

CROSS-REFERENCE TO RELATED APPLICATION

The present application is a continuation of and claims priority to U.S.application Ser. No. 17/493,024 filed Oct. 4, 2021, the contents ofwhich is hereby incorporated by reference in its entry.

RIGHTS OF THE GOVERNMENT

The invention described herein may be manufactured and used by or forthe Government of the United States for all governmental purposeswithout the payment of any royalty.

FIELD OF THE INVENTION

The present invention relates to a mechanochemical based synthesis ofperfluoropyridine monomers, polymers made using such monomers andmethods of making and using articles comprising such polymers.

BACKGROUND OF THE INVENTION

The current plate of monomers used to produce polymers is limited. Inparticular, the plate of monomers used to make polymers for hightemperature and low temperature applications is even more limited.Applicants' recognized that one of the reasons that many monomers cannotbe used in such applications is they either have weak bonds and thusfail at high temperature applications and if they have strong bonds theyare rigid and thus not suitable for low temperature applications. Basedon such recognition, Applicants developed perfluoropyridine monomers.Such perfluoropyridine monomers comprise covalent fluorine—carbon bondsthat provide the strength needed for high temperature applications andether moieties that provide the flexibility needed for low temperatureapplications. In addition, surprisingly such ether moieties not onlyprovide the desired low temperature flexibility but also providebackbone strength for the monomer via the ether's association withcarbons in the monomer's backbone that further increases the strengthneeded for high temperature applications without detracting from lowtemperature flexibility. A further advantage of the disclosedperfluoropyridine monomers is that they can be easily chemically tunedfor a specific application by pyridine positioning. All of theaforementioned performance application advantages are also found inpolymers comprising Applicants' perfluoropyridine-containing monomers.

In addition, to the aforementioned perfluoropyridine monomers,Applicants disclose a mechanochemical based synthesis for suchperfluoropyridine monomers. Such synthesis has a number of advantagesincluding, but not limited to, no need for solvent, no need for a heatsource to activate and maintain the reaction, synthesis flexibility asthe synthesis can be run as a batch, semi-batch or continuous processand, while not being bound by theory, Applicants believe that thesynthesis can be performed without the need for gravity.

SUMMARY OF THE INVENTION

The present invention relates to a mechanochemical based synthesis ofperfluoropyridine monomers, polymers made using such monomers andmethods of making and using articles comprising such polymers. Suchperfluoropyridine-containing monomers are easily chemically tuned havethe strength needed for high temperature applications and theflexibility needed for low temperature applications. In addition, to theaforementioned monomers, a mechanochemical based synthesis for suchperfluoropyridine monomers is provided. All of the aforementionedperformance application advantages are also found in polymers comprisingApplicants' perfluoropyridine monomers.

Additional objects, advantages, and novel features of the invention willbe set forth in part in the description which follows, and in part willbecome apparent to those skilled in the art upon examination of thefollowing or may be learned by practice of the invention. The objectsand advantages of the invention may be realized and attained by means ofthe instrumentalities and combinations particularly pointed out in theappended claims.

DETAILED DESCRIPTION OF THE INVENTION Definitions

Unless specifically stated otherwise, as used herein, the terms “a”,“an” and “the” mean “at least one”.

As used herein, the terms “include”, “includes” and “including” aremeant to be non-limiting.

As used herein, the words “about,” “approximately,” or the like, whenaccompanying a numerical value, are to be construed as indicating adeviation as would be appreciated by one of ordinary skill in the art tooperate satisfactorily for an intended purpose.

As used herein, the words “and/or” means, when referring to embodiments(for example an embodiment having elements A and/or B) that theembodiment may have element A alone, element B alone, or elements A andB taken together.

Unless otherwise noted, all component or composition levels are inreference to the active portion of that component or composition, andare exclusive of impurities, for example, residual solvents orby-products, which may be present in commercially available sources ofsuch components or compositions.

All percentages and ratios are calculated by weight unless otherwiseindicated. All percentages and ratios are calculated based on the totalcomposition unless otherwise indicated.

It should be understood that every maximum numerical limitation giventhroughout this specification includes every lower numerical limitation,as if such lower numerical limitations were expressly written herein.Every minimum numerical limitation given throughout this specificationwill include every higher numerical limitation, as if such highernumerical limitations were expressly written herein. Every numericalrange given throughout this specification will include every narrowernumerical range that falls within such broader numerical range, as ifsuch narrower numerical ranges were all expressly written herein.

Monomers, Compositions Monomers and Articles Comprising Same

For purposes of this specification, headings are not consideredparagraphs and thus this paragraph is paragraph fifteen of the presentspecification. The individual number of each paragraph above and belowthis paragraph can be determined by reference to this paragraph'snumber. In this paragraph fifteen, Applicants disclose a monomer havingthe following formula:

wherein

-   -   a) R₁ is a branched unsubstituted hydrocarbon, branched        unsubstituted hydrocarbon, branched substituted hydrocarbon or        unbranched substituted hydrocarbon;    -   b) each R₂ is independently fluorine, a branched unsubstituted        hydrocarbon, branched unsubstituted hydrocarbon, branched        substituted hydrocarbon or unbranched substituted hydrocarbon;    -   c) X is nitrogen or carbon and when the indice n is 0, X is        nitrogen and when X is carbon the indice n is 1; and    -   d) when n is 1, R₃ is fluorine.

Applicants disclose the monomer according to paragraph fifteen of thisspecification wherein:

-   -   a) for R₁ said branched unsubstituted hydrocarbon is an alkane,        an alkene, an alkyne, or an aromatic;    -   b) for R₁ said unbranched unsubstituted hydrocarbon is an        alkane, an alkene, an alkyne, or an aromatic;    -   c) for R₁ said branched substituted hydrocarbon comprises one or        more Si, Ge, Sn, pnictogen, chalcogen and/or halogen        substituents;    -   d) for R₁ said unbranched substituted hydrocarbon comprises one        or more Si, Ge, Sn, pnictogen, chalcogen and/or halogen        substituents;    -   e) for R₂ said branched unsubstituted hydrocarbon is an alkane,        an alkene, an alkyne, or an aromatic;    -   f) for R₂ said unbranched unsubstituted hydrocarbon is an        alkane, an alkene, an alkyne, or an aromatic;    -   g) for R₂ said branched substituted hydrocarbon comprises one or        more Si, Ge, Sn, pnictogen, chalcogen and/or halogen        substituents; and    -   h) for R₂ said unbranched substituted hydrocarbon comprises one        or more Si, Ge, Sn, pnictogen, chalcogen and/or halogen        substituents.

Applicants disclose the monomer according to paragraph sixteen of thisspecification wherein:

-   -   a) for R₁ said branched unsubstituted hydrocarbon is an alkane,        an alkene, an alkyne, or an aromatic; preferably for R₁ said        branched unsubstituted hydrocarbon is an alkene, an alkyne, or        an aromatic, more preferably for R₁ said branched unsubstituted        hydrocarbon is an aromatic;    -   b) for R₁ said un branched unsubstituted hydrocarbon is an        alkane, an alkene, an alkyne, or an aromatic; preferably for R₁        said unbranched unsubstituted hydrocarbon is an alkene, an        alkyne, or an aromatic, more preferably for R₁ said unbranched        unsubstituted hydrocarbon is an aromatic;    -   c) for R₁ said branched substituted hydrocarbon comprises one or        more Si, Ge, Sn, pnictogen, chalcogen and/or halogen        substituents; preferably for R₁ said branched substituted        hydrocarbon comprises one or more Si, N, P, O, S, Cl, Br, I        and/or F substituents; more preferably for R₁ said branched        substituted hydrocarbon comprises one or more N, O, I and/or F        substituents; most preferably for R₁ said branched substituted        hydrocarbon comprises one or more O and/or F substituents;    -   d) for R₁ said unbranched substituted hydrocarbon comprises one        or more Si, Ge, Sn, pnictogen, chalcogen and/or halogen        substituents; preferably for R₁ said unbranched substituted        hydrocarbon comprises one or more Si, N, P, O, S, Cl, Br, I        and/or F; more preferably for R₁ said unbranched substituted        hydrocarbon comprises one or more N, O, I and/or F substituents,        most preferably for R₁ said branched substituted hydrocarbon        comprises one or more O and/or F substituents;    -   e) for R₂ said branched unsubstituted hydrocarbon is an alkane,        an alkene, an alkyne, or an aromatic; preferably for R₂ said        branched unsubstituted hydrocarbon is an alkene, an alkyne, or        an aromatic, more preferably for R₂ said branched unsubstituted        hydrocarbon is an aromatic;    -   f) for R₂ said un branched unsubstituted hydrocarbon is an        alkane, an alkene, an alkyne, or an aromatic; preferably for R₂        said unbranched unsubstituted hydrocarbon is an alkene, an        alkyne, or an aromatic, more preferably for R₂ said unbranched        unsubstituted hydrocarbon is an aromatic;    -   g) for R₂ said branched substituted hydrocarbon comprises one or        more Si, Ge, Sn, pnictogen, chalcogen and/or halogen        substituents; preferably for R₂ said branched substituted        hydrocarbon comprises one or more Si, N, P, O, S, Cl, Br, I        and/or F substituents; more preferably for R₂ said branched        substituted hydrocarbon comprises one or more N, O, I and/or F        substituents; most preferably for R₂ said branched substituted        hydrocarbon comprises one or more O and/or F substituents; and    -   h) for R₂ said unbranched substituted hydrocarbon comprises one        or more Si, Ge, Sn, pnictogen, chalcogen and/or halogen        substituents; preferably for R₁ said unbranched substituted        hydrocarbon comprises one or more Si, N, P, O, S, Cl, Br, I        and/or F; more preferably for R₂ said unbranched substituted        hydrocarbon comprises one or more N, O, I and/or F substituents,        most preferably for R₂ said unbranched substituted hydrocarbon        comprises one or more O and/or F substituents.

Applicants disclose the monomer according to paragraphs fifteen throughseventeen of this specification wherein R₁ and each R₂ are independentlya perfluoropolyalkylether (PFPAE), aryl or alkyl moiety.

Applicants disclose the monomer according to paragraphs fifteen througheighteen of this specification wherein R₁ and each R₂ each have aformula selected from Formulas 1 through 18 below:

wherein the indices for said Formulas 1 through 18 are as follows

-   -   a) the indice m is 0 to 100, preferably the indice m is 0 to 10,        more preferably the indice m is 0 to 5; in one aspect m the        indice m is 1 to 100;    -   b) the indice n is 0 to 100, preferably the indice n is 1 to 50,        more preferably the indice n is 1 to 10;    -   c) the indice p is 0 to 100, preferably the indice p is 1 to 50,        more preferably the indice p is 1 to 10;    -   d) the indice y is 0 to 100, preferably the indice y is 1 to 50,        more preferably the indice y is 1 to 10; and    -   e) the indice z is 1 to 6, preferably the indice z is 1 to 5,        more preferably the indice z is 2 to 4.

Applicants disclose a composition comprising the monomer according toparagraphs fifteen through nineteen of this specification, saidcomposition being a polymer network, a lubricant or an oxidizer.

Applicants disclose the composition of paragraph twenty of thisspecification, said composition being a polymer network.

Applicants disclose the composition of paragraph twenty of thisspecification, wherein said polymer network is a homopolymer network.

Applicants disclose an article comprising the polymer network accordingto paragraphs twenty through twenty-two of this specification, saidarticle being a propellant binder, a deicing coating, a chemicallyprotective coating, a friction reducing coating, gasket material or aseparation membrane material.

Applicants disclose an article comprising the polymer network accordingto paragraphs twenty through twenty-two of this specification, saidarticle being an aerospace vehicle, a motor vehicle, a separation unitor a consumer good. Non-limiting examples of aerospace vehicles arefound in Table 1 below.

TABLE 1 Aerospace Vehicle Type and Modes of Guidance, Navigation, andControl Vehicle GNC Methods Maneuver Method AIR Weather Balloonradiosonde, theodolite pressure inside balloon Manned aircraftaltimeter, inertial navigation system thrust, flight control (INS),Global Positioning System (GPS) surfaces Unmanned aircraft altimeter,INS, GPS thrust, flight control surfaces Quadcopter visual sensor, GPSpropeller(s) Airborne Missile altimeter, INS, GPS thrust, flight controlsurfaces AEROSPACE Scientific Balloon star camera, altimeter pressureinside balloon Sounding Rocket ring laser gyro, altimeter,accelerometers thrust, flight control surfaces Space Shuttlehuman-in-the-loop, star camera thrust, flight control surfaces LaunchVehicle INS, ring laser gyro, altimeter, thrust, flight control (Rocket)accelerometers surfaces Ballistic Missile INS, GPS thrust, flightcontrol surfaces SPACE Satellite star camera, sun sensor, horizonsensor, thruster, electric propulsion, GPS magnetorquer, momentum wheelSpace Station human, star camera, sun sensor, horizon thruster, electricpropulsion, sensor, GPS magnetorquer, momentum wheel Interplanetary starcamera, sun sensor thruster, electric propulsion, Vehicle momentum wheel

Examples of flight control surfaces include fins, ailerons, elevatorsand thrust includes the two-directional thrust force, as well as anygimbaled thrust vectoring the vehicle is capable of generating.

For generating monomers that have low glass transition temperatures, R₁should be a PFPAE. This would also allow the monomer to be inserted intoother materials such as bisphenol A and bisphenol AF, as examples, inorder to enhance their temperature performance. Also, if R₁ is a PFPAE,and if 1,2-diphenylethyne or phenyl ethyne is inserted into the R₂positions, this would afford thermoset polymers. In general, if thematerials needs to be stiffer and stronger, a cross-linking monomerwould be required, thus PFPAEs should be placed in both the R₁ and R₂positions. If R₁ is aryls or alkyls then these materials can beradically polymerized through the alkene, reacted with thiols to formthiol-ene thermoset materials or polymerized with H-PDMS [poly(dimethylsiloxanes] or octadimethylhydrosilyl cubic siloxane (OctaSilanePOSS) catalyzed with platinum, as examples. If aryls or alkyls are placein both R₁ and R₂ positon, then this provides for cross-linkingcapabilities, just like PFPAEs. There is also the opportunity foralkynes to thermally cure to form thermoset resins. Therefore, if aryland alkyls are also inserted into the R₂ position, this providescross-linking abilities.

Process of Making Monomers and Polymer Networks Comprising Same

Applicants disclose a process of making the monomer of paragraphsfifteen through nineteen of this specification, said process comprising:

-   -   a) combining a nucleophile, a carbonate and a fluoro-substituted        aromatic in a mill to form a combined composition or combining a        nucleophile, a carbonate and a fluoro-substituted aromatic to        form a combined composition; and    -   b) milling the said combined composition.

Applicants disclose the process according to paragraph twenty-six ofthis specification, wherein:

-   -   a) said nucleophile is selected from the group consisting of a        tetrel, a pnictogen, a chalcogen and mixtures thereof,        preferably said nucleophile is selected from the group        consisting of a tetrel comprising carbon and/or silicon, a        pnictogen comprising nitrogen, and/or phosphorus, a chalcogen        comprising oxygen and/or sulfur and mixtures thereof, more        preferably said nucleophile is selected from the group        consisting of a tetrel comprising carbon, a pnictogen comprising        nitrogen, a chalcogen comprising oxygen and mixtures thereof;    -   b) said carbonate is selected from the group consisting of        potassium carbonate and cesium carbonate, preferably said        carbonate comprises cesium carbonate; and    -   c) said fluoro-substituted aromatic material is selected from        the group consisting of a fluoro-substituted aromatic molecule,        a polymer comprising a fluoro-substituted aromatic moiety and        mixtures thereof, preferably said fluoro-substituted aromatic        material is selected from the group consisting of        perfluoropolyalkylether-, fluoro-silicon, and a polymer        comprising a perfluroalkyl moiety, more preferably said        fluoro-substituted aromatic material comprises        perfluoropolyalkylethers.

Applicants disclose the process according to paragraphs twenty-sixthrough twenty-seven of this specification, wherein said milling isconducted using a ball mill, a planetary ball mill, vibration ball mill,a stirring ball mill, a pin ball mill, a rolling ball mill, or an augermill, preferably said milling is conducted using a ball mill.

Applicants disclose a process of making the polymer network according toparagraphs twenty through twenty-two of this specification, said processcomprising combining a nucleophile and a monomer as detailed in toparagraphs fifteen to nineteen of this specification in a mill to form acombined composition or combining a nucleophile and a monomer accordingto paragraphs twenty through twenty-two of this specification to form acombined composition and then placing said combined composition in amill and milling the said combined composition.

Applicants disclose the process of paragraph twenty-eight of thisspecification wherein nucleophile is selected from the group consistingof nucleophile is selected from the group consisting of a tetrel, apnictogen, a chalcogen and mixtures thereof, preferably said nucleophileis selected from the group consisting of a tetrel comprising carbonand/or silicon, a pnictogen comprising nitrogen, and/or phosphorus, achalcogen comprising oxygen and/or sulfur and mixtures thereof, morepreferably said nucleophile is selected from the group consisting of atetrel comprising carbon, a pnictogen comprising nitrogen, a chalcogencomprising oxygen and mixtures thereof.

Applicants disclose the process of paragraph twenty-nine of thisspecification wherein a second monomer other than a monomer according toparagraph fifteen of this specification is added to said ball millduring said process, preferably said second monomer is added after saidcombined composition is formed.

Materials that are needed to produce the monomers disclosed and/orclaimed by Applicants in this specification can be purchased fromcompanies such as: (Oakwood chemicals 730 Columbia Hwy. N, Estill, S.C.29918); 4-bromophenol, 1,1,1-tris(4-hydroxylphenyl) ethane (TCI America9211 North Harborgate Street Portland, Oreg. 97203); polyethylene glycol(PEG-200), bisphenol A, bisphenol AF, eugenol, allyl alcohol, potassiumfluoride, calcium carbonate, lithium carbonate, potassium carbonate, andcesium carbonate (Alfa-Aesar, 2 Radcliff Rd, Tewksbury, Mass. 01876);diethylether; 2H,3H-perfluoropentane (Vertrel™ Chemours, The ChemoursCompany, 1007 Market Street P.O. Box 2047, Wilmington, Del. 19899);perfluoropyridine (SynQuest, SynQuest Laboratories, Inc., 13201 RachaelBlvd, Rt 2054, Alachua Fla. 32615); L-9939 perfluoropolyether diol (MACHI Inc., 340 E Church Rd, King of Prussia, Pa. 19406); Krytox® methylenealcohol (Chemours, The Chemours Company, 1007 Market Street P.O. Box2047, Wilmington, Del. 19899).

EXAMPLES

The following examples illustrate particular properties and advantagesof some of the embodiments of the present invention. Furthermore, theseare examples of reduction to practice of the present invention andconfirmation that the principles described in the present invention aretherefore valid but should not be construed as in any way limiting thescope of the invention.

Example 1: Cesium carbonate (0.3495 g, 1.1 mmol), p-bromophenol (0.1909g 1.1 mmol), and pentafluoropyridine (0.2721 g. 1.6 mmol) was added tothe capsule and agitated for 20 minutes. GC results: retention time (%)9.780 min (97.9%) mono, 15.439 min (1.6%) di.

Example 2: Cesium carbonate (0.3412 g, 1.0 mmol), p-bromophenol (0.1910g 1.1 mmol), and pentafluoropyridine (0.2759 g. 1.6 mmol) was added tothe capsule and agitated for 1 minute. GC results: retention time (%)7.742 min (1.3%) Br-PhOH, 9.766 min (98.4%) mono, 15.428 min (0.3%) di.

Example 3: Cesium carbonate (0.3600 g, 1.1 mmol), p-bromophenol (0.4051g 2.3 mmol), and pentafluoropyridine (0.1844 g. 1.1 mmol) was added tothe capsule and agitated for 1 minute. GC results: retention time (%)7.728 min (41.8%) Br-PhOH, 9.742 min (57.2%) mono, 15.412 (1.0%) di.

Example 4: Potassium carbonate (0.1586 g, 1.1 mmol), p-bromophenol(0.2016 g 1.2 mmol), and pentafluoropyridine (0.2875 g. 1.7 mmol) wasadded to the capsule and agitated for 1 minute. GC results: retentiontime (%) 7.743 min (92.5%) Br-PhOH, 9.753 min (7.522%) mono.

Example 5: This is a comparative example. Lithium carbonate (0.0807 g,1.1 mmol), p-bromophenol (0.2215 g 1.3 mmol), and pentafluoropyridine(0.2853 g. 1.7 mmol) was added to the capsule and agitated for 1 minute.No reaction. GC results: retention time (%) 7.719 min (100%) Br-PhOH.

Example 6: This is a comparative example. Celite 545 (0.0863 g),p-bromophenol (0.1851 g), and pentafluoropyridine (0.2814 g. 1.7 mmol)was added to the capsule and agitated for 1 minute. No reaction. GCresults: retention time (%) 7.719 min (100%) Br-PhOH.

Example 7: This is a comparative example. Silica (0.0898 g),p-bromophenol (0.2128 g), and pentafluoropyridine (0.2899 g. 1.7 mmol)was added to the capsule and agitated for 1 minute. No reaction. GCresults: retention time (%) 7.719 min (100%) Br-PhOH.

Example 8: This is a comparative example. Calcium carbonate (0.1180 g,1.2 mmol), p-bromophenol (0.2005 g 1.2 mmol), and pentafluoropyridine(0.3173 g. 1.9 mmol) was added to the capsule and agitated for 1 minute.No reaction. GC results: retention time (%) 7.719 min (100%).

Example 9: Cesium carbonate (0.3581 g, 1.1 mmol), allyl alcohol (0.3952g 6.8 mmol), and pentafluoropyridine (0.1949 g. 1.2 mmol) was added tothe capsule and agitated for 1 minute. GC results: retention time (%)1.649 min (11.5%) Allyl-OH, 1.832 min (10.6%) PFP, 5.456 min (39.6%)mono adduct.

Example 10: Cesium carbonate (0.3629 g, 1.1 mmol), Krytox® methylenealcohol (1.0000 g, 0.5 mmol), and pentafluoropyridine (0.3640 g. 2.2mmol) was added to the capsule and agitated for 1.5 minutes. GC results:retention time (%) 5.452-8.673 min (10.6%) HEC, 8.967-11.942 min (89.4%)Krytox® CH₂OC₅F₄N.

Example 11: Cesium carbonate (0.3650 g, 1.1 mmol), Eugenol (0.1764 g,1.1 mmol), and pentafluoropyridine (0.7790 g. 4.6 mmol) was added to thecapsule and agitated for 1 minute. GC results: retention time (%) 10.752min (100%) mono-adduct.

Example 12: Cesium carbonate (0.3600 g, 1.1 mmol), MACH I (1.0500 g, 1.0mmol), and pentafluoropyridine (0.3700 g. 2.2 mmol) was added to thecapsule and agitated for 1 minute. GC results: retention time (%)2.158-6.715 min (4%) HEC, 7.347-9.758 min (16.6%) mono-, 10.765-12.346(77.3%) di-adduct, 13.390-16.289 min (6.1%) cross-linked.

Example 13: Cesium carbonate (0.3500 g, 1.1 mmol), Eugenol (0.1886 g,1.1 mmol), and pentafluoropyridine (0.0577 g. 0.3 mmol) was added to thecapsule and agitated for 1 minute. GC results: retention time (%) 8.320min (37.5%) Eugenol, 10.768 min (10.3%) mono, 16.416 (52.2%) di. 19F-NMRresults: 16% mono-, 80.8% di-, and 3.2% tri-adduct.

Example 14: Cesium carbonate (0.3700 g, 1.1 mmol), Eugenol (0.1827 g,1.1 mmol), and pentafluoropyridine (0.0616 g. 0.4 mmol) was added to thecapsule and agitated for 5 minutes. GC results: retention time (%) 8.292min (21.3%) Eugenol, 16.416 (78.7%) di. 19F-NMR results: 17% di-, and83% tri-adduct.

Example 15: Cesium carbonate (0.3700 g, 1.1 mmol), Eugenol (0.1438 g,0.9 mmol), and pentafluoropyridine (0.0503 g. 0.3 mmol) was added to thecapsule and agitated for 1 minute. GC results: retention time (%) 8.317min (9.2%) Eugenol, 16.414 (90.8%) di. 19F-NMR results: 18.6% di-, and81.4% tri-adduct.

Example 16: This is a comparative example. Potassium fluoride (0.1800 g,3.1 mmol), Eugenol (0.5000 g, 3.0 mmol), and pentafluoropyridine (0.1500g. 0.9 mmol) was added to the capsule and agitated for 1 minute. Noreaction. GC results: retention time (%) 8.292 min (100%) Eugenol.19F-NMR results: 100% PFP.

Example 17: This is a comparative example. Cesium carbonate (0.3663 g,1.1 mmol), Eugenol (0.1931 g, 1.2 mmol), and hexafluorobenzene (0.4022g, 2.2 mmol) was added to the capsule and agitated for 1 minute. Noreaction. GC results: retention time (%) 8.320 min (93.6) Eugenol,10.707 min (6.4%) mono. 19F-NMR results: 100% PFP.

Example 18: Cesium carbonate (0.3517 g, 1.1 mmol), Fluorolink E10H(1.0046 g, 1.0 mmol), and pentafluoropyridine (0.3729 g. 2.2 mmol) wasadded to the capsule and agitated for 1 minute. 19F-NMR results: 70.3%di and 29.7% mono.

Example 19: A fluoropolymeric system was made as follows: Cesiumcarbonate (0.3517 g, 1.1 mmol), Fluorolink E10H (1.0046 g, 0.56 mmol),and pentafluoropyridine (0.3729 g. 2.2 mmol) was added to the capsuleand agitated for 1 minute. 19F-NMR results: 70.3% di and 29.7% mono. Thefluoropolymeric system is used as a lubricant additive by adding thefluoropolymeric system to a lubricant. The fluoropolymeric system isalso used as a lithium battery additive by adding the fluoropolymericsystem to a lithium battery wherein serves as electrolyte. Thefluoropolymeric system is also used as a viscosity modifier by addingthe fluoropolymeric system to an oil. The fluoropolymeric system is alsoused as an anticorrosive intermediate by adding the fluoropolymericsystem to a lubricant which is applied to a metal.

The fluoropolymeric system of Example 19 is used as a lubricant additiveby adding the fluoropolymeric system to a lubricant.

Every document cited herein, including any cross referenced or relatedpatent or application and any patent application or patent to which thisapplication claims priority or benefit thereof, is hereby incorporatedherein by reference in its entirety unless expressly excluded orotherwise limited. The citation of any document is not an admission thatit is prior art with respect to any invention disclosed or claimedherein or that it alone, or in any combination with any other referenceor references, teaches, suggests or discloses any such invention.Further, to the extent that any meaning or definition of a term in thisdocument conflicts with any meaning or definition of the same term in adocument incorporated by reference, the meaning or definition assignedto that term in this document shall govern.

While the present invention has been illustrated by a description of oneor more embodiments thereof and while these embodiments have beendescribed in considerable detail, they are not intended to restrict orin any way limit the scope of the appended claims to such detail.Additional advantages and modifications will readily appear to thoseskilled in the art. The invention in its broader aspects is thereforenot limited to the specific details, representative apparatus andmethod, and illustrative examples shown and described. Accordingly,departures may be made from such details without departing from thescope of the general inventive concept.

What is claimed is:
 1. A monomer having the following formula:

wherein a) R₁ is a branched unsubstituted hydrocarbon, branchedunsubstituted hydrocarbon, branched substituted hydrocarbon orunbranched substituted hydrocarbon; b) each R₂ is independentlyfluorine, a branched unsubstituted hydrocarbon, branched unsubstitutedhydrocarbon, branched substituted hydrocarbon or unbranched substitutedhydrocarbon; c) X is nitrogen or carbon and when the indice n is 0, X isnitrogen and when X is carbon the indice n is 1; and d) when n is 1, R₃is fluorine.
 2. A monomer according to claim 1 wherein: a) for R₁ saidbranched unsubstituted hydrocarbon is an alkane, an alkene, an alkyne,or an aromatic; b) for R₁ said unbranched unsubstituted hydrocarbon isan alkane, an alkene, an alkyne, or an aromatic; c) for R₁ said branchedsubstituted hydrocarbon comprises one or more Si, Ge, Sn, pnictogen,chalcogen and/or halogen substituents; d) for R₁ said unbranchedsubstituted hydrocarbon comprises one or more Si, Ge, Sn, pnictogen,chalcogen and/or halogen substituents; e) for R₂ said branchedunsubstituted hydrocarbon is an alkane, an alkene, an alkyne, or anaromatic; f) for R₂ said unbranched unsubstituted hydrocarbon is analkane, an alkene, an alkyne, or an aromatic; g) for R₂ said branchedsubstituted hydrocarbon comprises one or more Si, Ge, Sn, pnictogen,chalcogen and/or halogen substituents; and h) for R₂ said unbranchedsubstituted hydrocarbon comprises one or more Si, Ge, Sn, pnictogen,chalcogen and/or halogen substituents.
 3. A monomer according to claim 2wherein: a) for R₁ said branched unsubstituted hydrocarbon is anaromatic; b) for R₁ said unbranched unsubstituted hydrocarbon is anaromatic; c) for R₁ said branched substituted hydrocarbon comprises oneor more O and/or F substituents; d) for R₁ said branched substitutedhydrocarbon comprises one or more O and/or F substituents; e) for R₂said branched unsubstituted hydrocarbon is an aromatic; f) for R₂ saidunbranched unsubstituted hydrocarbon is an aromatic; g) for R₂ saidbranched substituted hydrocarbon comprises one or more O and/or Fsubstituents; and h) for R₂ said unbranched substituted hydrocarboncomprises one or more O and/or F substituents.
 4. A monomer according toclaim 1 wherein R₁ and each R₂ are independently aperfluoropolyalkylether, aryl or alkyl moiety.
 5. A monomer according toclaim 1 wherein R₁ and each R₂ each have a formula selected fromFormulas 1 through 18 below:

wherein the indices for said Formulas 1 through 18 are as follows a) theindice m is 0 to 100; b) the indice n is 0 to 100; c) the indice p is 0to 100; d) the indice y is 0 to 100; and e) the indice z is 1 to
 6. 6. Acomposition comprising the monomer according to claim 1, saidcomposition being a polymer network, a lubricant or an oxidizer.
 7. Thecomposition of claim 6, said composition being a polymer network.
 8. Thecomposition of claim 7, wherein said polymer network is a homopolymernetwork.
 9. An article comprising the polymer network according to claim7 said article being a propellant binder, a deicing coating, achemically protective coating, a friction reducing coating, gasketmaterial or a separation membrane material.
 10. An article comprisingthe polymer network according to claim 7 said article being an aerospacevehicle, a motor vehicle, a separation unit or a consumer good.
 11. Aprocess of making the monomer of claim 1, said process comprising: a)combining a nucleophile, a carbonate and a fluoro-substituted aromaticin a mill to form a combined composition or combining a nucleophile, acarbonate and a fluoro-substituted aromatic to form a combinedcomposition; and b) milling said combined composition.
 12. The processaccording to claim 11, wherein: a) said nucleophile is selected from thegroup consisting of a tetrel, a pnictogen, a chalcogen and mixturesthereof; b) said carbonate is selected from the group consisting ofpotassium carbonate and cesium carbonate; and c) said fluoro-substitutedaromatic material is selected from the group consisting of afluoro-substituted aromatic molecule, a polymer comprising afluoro-substituted aromatic moiety and mixtures thereof.
 13. The processaccording to claim 11, wherein said milling is conducted using a ballmill, a planetary ball mill, vibration ball mill, a stirring ball mill,a pin ball mill, a rolling ball mill, or an auger mill.
 14. The processof making the polymer network of claim 6 said process comprisingcombining a nucleophile and a monomer according to claim 1 in a mill toform a combined composition or combining a nucleophile and a monomeraccording to claim 1 to form a combined composition and then placingsaid combined composition in a mill; and milling the said combinedcomposition.
 15. The process of claim 13 wherein nucleophile is selectedfrom the group consisting of nucleophile is selected from the groupconsisting of a tetrel, a pnictogen, a chalcogen and mixtures thereof.16. The process of claim 14 wherein a second monomer, other than amonomer according to claim 1, is added to said ball mill during saidprocess.
 17. The process of claim 16 wherein, said second monomer isadded after said combined composition is formed.